Reactions of the Cumyloxyl Radical with Secondary Amides. The Influence of Steric and Stereoelectronic Effects on the Hydrogen Atom Transfer Reactivity and Selectivity
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- 作者：Michela Salamone ; Federica Basili ; Riccardo Mele ; Marco Cianfanelli ; Massimo Bietti
- 刊名：Organic Letters
- 出版年：2014
- 出版时间：December 19, 2014
- 年：2014
- 卷：16
- 期：24
- 页码：6444-6447
- 全文大小：260K
- ISSN：1523-7052
文摘
A time-resolved kinetic study of the hydrogen atom transfer (HAT) reactions from secondary alkanamides to the cumyloxyl radical was carried out in acetonitrile. HAT predominantly occurs from the N-alkyl 伪-C鈥揌 bonds, and a >60-fold decrease in kH was observed by increasing the steric hindrance of the acyl and N-alkyl groups. The role of steric and stereoelectronic effects on the reactivity and selectivity is discussed in the framework of HAT reactions from peptides.